KR100272451B1 - Filter medium for removing phosphorous and method for preparing - Google Patents
Filter medium for removing phosphorous and method for preparing Download PDFInfo
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- KR100272451B1 KR100272451B1 KR1019970024381A KR19970024381A KR100272451B1 KR 100272451 B1 KR100272451 B1 KR 100272451B1 KR 1019970024381 A KR1019970024381 A KR 1019970024381A KR 19970024381 A KR19970024381 A KR 19970024381A KR 100272451 B1 KR100272451 B1 KR 100272451B1
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- South Korea
- Prior art keywords
- phosphorus
- soil
- weight
- water
- weight ratio
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 106
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title 1
- 239000002689 soil Substances 0.000 claims abstract description 117
- 230000008569 process Effects 0.000 claims abstract description 83
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 75
- 239000011574 phosphorus Substances 0.000 claims abstract description 75
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 74
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010304 firing Methods 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 5
- 238000010790 dilution Methods 0.000 claims 5
- 239000012895 dilution Substances 0.000 claims 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 4
- 239000002075 main ingredient Substances 0.000 claims 2
- 239000000945 filler Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 60
- 238000012851 eutrophication Methods 0.000 abstract description 27
- 238000000465 moulding Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 20
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 18
- 238000000746 purification Methods 0.000 abstract description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 5
- 150000004679 hydroxides Chemical class 0.000 abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 3
- 229910000358 iron sulfate Inorganic materials 0.000 abstract description 3
- 239000002585 base Substances 0.000 abstract 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 239000002956 ash Substances 0.000 description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000002699 waste material Substances 0.000 description 22
- 239000010802 sludge Substances 0.000 description 21
- 241000195493 Cryptophyta Species 0.000 description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 16
- 239000003610 charcoal Substances 0.000 description 14
- 239000003245 coal Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010276 construction Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 235000015097 nutrients Nutrition 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- -1 but among them Chemical compound 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000010813 municipal solid waste Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000005791 algae growth Effects 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 231100000676 disease causative agent Toxicity 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 240000003826 Eichhornia crassipes Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
본 발명은 수질정화를 위한 인 제거용 여재와 그 제조방법에 관한 것으로, 상세하게는 주로 소호(沼湖)나 하천수(河川水) 부영양화의 주 요인인 인(燐:Phosphorus)을 부영양화의 한계점인 0.02ppm 이하로 제거할 수 있는 인 제거용 여재를 제공하여 수질의 부영양화를 효과적으로 개선 또는 예방할 수 있도록 한 것으로서, 통상의 토양(土壤)에 과산화수소(H2O2), 차아염소산, 과산화물 중에 적어도 하나 이상을 첨가하는 공정과 황산(H2SO4), 염산(HCl) 등의 무기산 중에 적어도 하나 이상을 첨가하는 공정과 황산철(FeSO4, Fe2(SO4)3), 염화철(FeCl2, FeCl3), 황산알미늄(Al2(SO4)3), 황산칼슘(CaSO4), 염화칼슘(CaCl2) 중에 적어도 하나 이상을 첨가하는 공정과 알카리 금속, 알카리 토류 금속의 수산화물, 탄산화물, 산화물을 소성 후의 pH가 중성에 가깝게 되도록 첨가하는 공정과 철분을 첨가하는 공정과 이렇게 혼합한 원료를 성형, 소성 가공하여 제조토록 한 것에 요지가 있음.The present invention relates to a filter for removing phosphorus for water purification and a method for manufacturing the same. Specifically, the phosphorus (Phosphorus), which is a major factor of Soho or river water eutrophication, is a limiting point of eutrophication. It provides phosphorus removal media that can remove below 0.02ppm to effectively improve or prevent eutrophication of water quality. At least one of hydrogen peroxide (H 2 O 2 ), hypochlorous acid, and peroxide in ordinary soil The process of adding the above, and the process of adding at least one of inorganic acids such as sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl) and iron sulfate (FeSO 4 , Fe 2 (SO 4 ) 3 ), iron chloride (FeCl 2 , FeCl 3 ), the addition of at least one of aluminum sulfate (Al 2 (SO 4 ) 3 ), calcium sulfate (CaSO 4 ), calcium chloride (CaCl 2 ) and hydroxides, carbonates, oxides of alkali metals and alkaline earth metals Even if the pH after firing is close to neutral There is a base to which ever produced by molding, the plastic working step and the raw material thus mixed is added to the process, iron is added.
Description
제1도는 본 발명의 개략적인 공정도.1 is a schematic process diagram of the present invention.
[발명의 목적][Purpose of invention]
본 발명은 수질정화를 위한 인 제거용 여재와 그 제조방법에 관한 것으로, 상세하게는 주로 소호(沼湖)나 하천수 부영양화의 주 요인인 인(燐:Phosphorus)을 부영양화의 한계점인 0.02ppm 이하로 제거할 수 있는 인 제거용 여재를 제공하여 부영양호(富營養湖) 등의 수질을 효과적으로 정화, 개선할 수 있도록 한 것이다.The present invention relates to a filter for removing phosphorus for water purification and a method for manufacturing the same. Specifically, phosphorus (Phosphorus), which is a major factor of Soho or river water eutrophication, is less than 0.02 ppm, which is the limit of eutrophication. By providing a phosphorus removal media that can be removed, it is possible to effectively purify and improve the water quality, such as eutrophic lakes.
[발명이 속하는 기술분야 및 그 분야의 종래기술][Technical field to which the invention belongs and the prior art in that field]
1. 부영양화의 가장 중요한 인자로서의 인1. Phosphorus as the most important factor of eutrophication
부영양화(雷營養化;Eutrophication - 조류의 번식에 의해 호소(湖酒)나 하천(河川)수의 영양염류 농도가 높아짐에 따라 수질이 빈영양에서 부영양으로 변화하는 것)의 원인물질은 일반적으로 유기물(BOD,COD), 질소, 인으로 분류되고 있다.Eutrophication-A source of eutrophication-changes in water quality from poor to eutrophic as the concentration of nutrients in lakes and rivers increases due to algal blooms. Organic substances (BOD, COD), nitrogen, and phosphorus are classified.
이것은 부영양화의 현상면에서 유해한 물질과 원인면에서 영향이 큰 물질로 분류할 수 있다.It can be classified as a harmful substance in the phenomenon of eutrophication and a substance having a great influence in the cause.
[부영양화의 현상과 물질][Phenomena and substances of eutrophication]
부양양화 현상은 국내의 많은 내수면 즉, 호소와 하천의 물에서 나타나고 있으며, 수질의 오염 및 악취문제가 유발되고 있다.The flotation phenomena occur in many domestic water surfaces, namely lakes and streams of water, causing water pollution and odor problems.
그 주된 원인물질은 폭발적으로 증식하여 수면을 완전히 덮고 있는 조류(藻類)와 그것의 부패물인 유기물이다.Its main causative agents are algae, which explode and fully cover the surface of water, and organic matter, its decay.
조류는 물속에서 질소와 인을 흡수하여 증식하며, 죽어 부패하여 물속에 그것을 환원시켜 다시 조류의 영양원이 된다.Algae absorb nitrogen and phosphorus in the water, multiply, die, decay, reduce it in water, and become nutrient sources for algae.
이와 같은 과정이 지속적으로 순환하여 수질의 오염과 악취의 원인물질인 조류와 유기물이 증가한다.This process continues to circulate, leading to an increase in algae and organics, which are the causes of water pollution and odors.
따라서 상기와 같이 발생된 조류를 제거하더라도 원인물질인 질소와 인을 제거하지 않는 한 곧 조류는 지속적으로 증식한다.Therefore, even if the algae generated as described above, algae will continue to multiply as long as the causative agents nitrogen and phosphorus are not removed.
이러한 관계로 호소와 하천에 유입되는 유입수 자체의 오염보다도 호소와 하천에 서 조류에 의해 발생되는 부영양화로 인한 자생 오염이 훨씬 심각한 경우도 허다하다.For this reason, autonomous pollution caused by eutrophication caused by algae in the lakes and rivers is much more serious than pollution of the influent water flowing into the lakes and rivers.
[부영양화의 원인과 물질][Causes and substances of eutrophication]
부영양화 원인물질은 조류의 영양원인 질소와 인이다.The eutrophic agents are nitrogen and phosphorus, algae's nutrient sources.
일부의 조류는 물 속의 초산(醋酸)태 또는 암모니아태 질소뿐 만 아니라 공중(空中) 질소도 흡수하여 영양원으로 사용하는 경우도 있지만, 인은 물속에서만 섭취할수 있다.Some algae absorb not only acetic acid or ammonia nitrogen in water, but also use it as a nutrient for air, but phosphorus can only be consumed in water.
따라서 조류는 물속에 인이 없으면 증식이 불가능하기 때문에 인을 부영양화의 제한인자(制限因子)라고 한다.Therefore, algae is called limiting factor of eutrophication because algae cannot grow without phosphorus in water.
[인이 조류에 미치는 영향][Influence of Phosphorus on Algae]
조류가 증식하기 위해 필요한 물질은 유기물질, 질소, 인으로 이를 중량비로 환산할 경우 100∼200 : 10 : 1 정도이다.Materials required for algae growth are organic matter, nitrogen, and phosphorus in terms of weight ratio of 100-200: 10: 1.
그러나 조류는 물속에 유기물과 질소가 없더라도 공중질소를 영양원으로 받아들임과 동시에 광합성(光合成)으로 유기물을 생산하여 물속의 질소와 유기물의 양을 증가시켜 부영양화 현상이 진행되지만, 인의 경우는 위에서 언급한 바와 같이 물속에 용해되어 있는 것만으로 조류의 증식에 필요한 인을 공급하게 된다.However, algae have no organic matter and nitrogen in the water, but also accept nitrogen as a nutrient source and produce organic matter by photosynthesis, increasing the amount of nitrogen and organic matter in the water, but eutrophication proceeds. Just dissolved in the water to supply the phosphorus necessary for algae growth.
그러므로 조류의 증식은 물속에 용해되어 있는 인의 양에 따라 결정된다.Therefore, algal growth depends on the amount of phosphorus dissolved in water.
즉, 물속에 인이 1단위 있으면, 지속적인 조류의 번식에 의해 물 속의 질소는 10단위가, 물 속의 유기물은 100∼200단위가 될 때까지 증가한 후 평형상태에 도달하게 된다.That is, if there is 1 unit of phosphorus in the water, by increasing the breeding of algae, nitrogen in the water increases until 10 units and organic matter in the water reaches 100 to 200 units and reaches an equilibrium state.
예를 들면 물 속에 인이 1ppm 존재하면 질소는 10ppm이 되며 유기물질은 100∼200ppm이 된다.For example, when 1 ppm of phosphorus is present in water, nitrogen is 10 ppm and organic matter is 100-200 ppm.
이상과 같이 인은 부영양화를 결정하는 가장 중요한 물질임을 알 수 있다.As described above, it can be seen that phosphorus is the most important substance for determining eutrophication.
그러나 인은 위에서 설명한 바와 같이 물 속에 미량만 존재하여도 부영양화는 진행되므로 인의 제거에 상당한 어려움이 있다.However, as described above, even if only a small amount is present in the water, eutrophication proceeds, so there is considerable difficulty in removing phosphorus.
부영양화가 발생되지 않는 인의 한계점은 0.02ppm 이하이므로 물 속의 인의 함량을 0.02ppm 이하로 제거할 때까지 부영양화는 진행한다.The limit of phosphorus without eutrophication is 0.02 ppm or less, so eutrophication proceeds until the phosphorus content in water is removed to 0.02 ppm or less.
2. 종래 수처리법의 인 제거법과 그 문제점2. Phosphorus removal method and problems of conventional water treatment
[화학적처리법][Chemical Treatment]
응집제인 Al염, Fe염 분말 또는 용액의 첨가로 물속에 용해되어 있는 총 인(T-P)의 양을 0.5ppm까지 제거시키는 것이 가능하다.It is possible to remove the total amount of phosphorus (T-P) dissolved in water by addition of Al salt, Fe salt powder or a solution which is a flocculant to 0.5 ppm.
또한, Ca염의 첨가로 물속에 용해되어 있는 총 인(T-P)의 양을 1.0ppm까지 처리 가능하며 3차 처리용으로는 0.1ppm까지 가능하나 이 방법은 5㎛ 이하의 마이크로 플록(Micro Flog)의 분리가 필요하며, 다량의 슬러지(Sludge)가 발생하므로 이를 적용시키는 것은 기술적으로 어렵고, 과다한 처리 비용이 발생한다.In addition, it is possible to treat the total amount of phosphorus (TP) dissolved in water by the addition of Ca salt up to 1.0 ppm and up to 0.1 ppm for the tertiary treatment. Separation is necessary, and a large amount of sludge is generated, so it is technically difficult to apply and excessive processing costs are incurred.
처리공정은 pH조정조(調整槽), 혼화조(混和槽), 응집조(凝集槽), 침전조(沈澱槽) 등을 순차적으로 거치며, 침전조에서 발생하는 침전물인 슬러지(Sludge)를 처리하는 장치가 별도로 필요로 하며, 이렇게 처리한 슬러지(Sludge)는 폐기물로 처리하여야 한다.The treatment process goes through a pH adjustment tank, a mixing tank, a flocculation tank, a sedimentation tank, etc. sequentially, and a device for treating sludge, which is a precipitate generated in the sedimentation tank, is provided. It is required separately and the sludge treated in this way should be disposed of as waste.
그러므로 그 설비는 대형화되고 유지비용이 과다할 뿐 만 아니라 제거효율이 낮아 부영양화를 막기는 거의 불가능하다.Therefore, the facility is not only large and large in maintenance costs, but also low in elimination efficiency, making it almost impossible to prevent eutrophication.
[생물학적처리법][Biological treatment]
혐기(嫌氣)성 미생물과 호기(好氣)성 미생물 처리법을 적절하게 이용하여 통상의 인 함유율의 2∼4배의 인을 폴리 인산염(Polyphosphate)의 형태로 미생물 슬러지(Sludge) 중에 축적시키는 기술이며, T-P를 1∼2ppm까지 처리가 가능하다.It is a technology that accumulates 2-4 times of phosphorus in the form of polyphosphate in the form of polyphosphate by appropriately using anaerobic and aerobic microorganism treatment methods. , TP can be processed to 1-2ppm.
처리공정은 pH조정조, 폭기조(혐기조), 침전조 등을 순차적으로 거치며, 침전조에서 발생하는 침전물인 슬러지(Sludge)를 처리하는 장치가 별도로 필요하고 이렇게 처리한 슬러지 (Sludge)는 폐기물로 처리하여야 한다.In the treatment process, pH adjusting tank, aeration tank, and sedimentation tank are sequentially processed, and a device for treating sludge, which is a sediment generated in the sedimentation tank, is required separately.
그러므로 그 설비도 역시 대형화되고 유지비용이 과다해질 뿐 만 아니라 제거효율이 낮아 부영양화를 막기는 거의 불가능하다.Therefore, the facility is not only large and large, and the maintenance cost is high, but also the removal efficiency is low, making it almost impossible to prevent eutrophication.
3. 부영양화된 호수 및 하천의 기존 정화법3. Conventional purification of eutrophic lakes and streams
[준설 작업에 의한 정화][Cleaning by dredging work]
각종 영양염에 의한 오염된 바닥의 퇴적층이 10∼50cm이상이므로 준설비용이 많이 들고, 준설 토사의 처리가 곤란하다.Since the sediment layer of the soil contaminated by various nutrients is 10-50 cm or more, it is used for a dredging facility and it is difficult to process dredged soil.
또한, 준설에 따른 지속적인 수질개선 효과를 기대할 수 없다.In addition, continuous water quality improvement from dredging cannot be expected.
[모래층 등의 여과에 의한 정화][Cleaning by filtration of sand layer, etc.]
유입수의 조건에 따라 일정하지는 않으나, 부유성 유기물의 제거율은 20∼50% 정도되나 용해성 인은 전혀 제거가 되지 않는다.Although not constant depending on the conditions of the influent, the removal rate of suspended organics is about 20-50%, but soluble phosphorus is not removed at all.
즉, 탁도 및 일부 입도가 큰 유기물질의 제거는 가능하나, 용해성 영양염류의 제거가 불가능하므로 부영양화의 진행을 막을 수는 없다.In other words, it is possible to remove turbidity and some large-sized organic matter, but it is impossible to remove soluble nutrients, so it is impossible to prevent eutrophication.
[미생물 접촉법에 의한 생물학적 정화][Biological Purification by Microbial Contact Method]
유입수의 유기물 제거율은 40∼70%정도이며, 용해성 인의 제거율을 10∼40% 정도이므로 유기물의 제거에는 다소 효과가 있으나, 인의 제거율이 낮아 부영양화를 막을 수 는 없다.The removal rate of organic matter in the influent is about 40 ~ 70%, and the removal rate of soluble phosphorus is about 10 ~ 40%, so it is effective to remove organic matter. However, low phosphorus removal rate cannot prevent eutrophication.
[부레옥잠 등의 배양에 의한 인의 회수][Recovery of phosphorus by cultivation of water hyacinth]
대규모 배양으로 인의 회수가 어느 정도 가능하나, 그 회수는 표면에서만 이루어지므로 보조적인 효과를 기대할 수 있으나 주된 처리법으로는 적용이 불가능하며 지속적인 수거 및 처리작업이 요구된다.Although large-scale cultivation of phosphorus can be recovered to some extent, the recovery is only performed on the surface, and thus an auxiliary effect can be expected. However, it is not applicable to the main treatment method and requires continuous collection and treatment.
[조류의 회수][Collection of birds]
조류의 회수에 따른 인의 제거는 탈수한 조류의 총 중량 중 인의 함유량은 0.15% 정도에 불가하므로, 조류 제거에 따른 일시적인 효과는 기대할 수 있으나, 인제거를 목적으로 하는 데는 보조적인 역할만 기대할 수 있으므로 주된 처리법으로는 적용이 거의 불가능하다.The removal of phosphorus by the recovery of algae is not possible at 0.15% of the total weight of dehydrated algae, so the temporary effect of the removal of algae can be expected, but only a secondary role can be expected for the purpose of phosphorus removal The main treatment is almost impossible to apply.
[폭기법에 의한 정화][Purification by aeration method]
부영양화된 물에 공기를 주입하여 용존산소를 높혀 유기물을 산화시키고, 호기성 상태에서의 인의 용출량을 줄이는 것으로 부영양화의 진행을 부분적으로 억제하는 것은 가능하나 부영양화를 막을 수는 없다.It is possible to partially suppress the progress of eutrophication by injecting air into eutrophicated water to increase dissolved oxygen to oxidize organic matter and to reduce the elution of phosphorus in an aerobic state, but it cannot prevent eutrophication.
[살균법에 의한 정화][Purification by Sterilization Method]
오존 및 자외선 등을 이용한 살균법(살조법)은 일시적인 조류 제거에는 매우 효과적이나 물 속에 인을 포함한 영양염류가 존재하는 한 곧 부영양화는 진행된다.Sterilization using ozone and ultraviolet light (algae) is very effective for temporary algae removal, but eutrophication will proceed as soon as nutrients, including phosphorus, are present in the water.
[발명이 이루고자 하는 기술적 과제][Technical problem to be achieved]
전술한 바와 같이 종래의 인 제거 기술로는 인의 농도를 부영양화의 한계점인 0.02ppm이하로 정화 시키는 것이 불가능하였던 바, 본 발명은 고성능의 인제거용 여재를 사용하여 인의 농도를 부영양화의 분기점 이하인 0.02ppm이하 까지 제거가 가능하게 할뿐만 아니라 저렴한 시설비와 작은 면적에도 설치가 가능하게 하여 부영양화 방지에 효율적으로 사용될 수 있도록 한 것이다.As described above, it was not possible to purify the concentration of phosphorus below 0.02 ppm, which is the limit of eutrophication, by using the conventional phosphorus removal technique. The present invention uses a high-performance phosphorus removal media to adjust the concentration of phosphorus below 0.02 ppm, which is below the branch point of eutrophication. Not only can it be removed, but also it can be used to prevent eutrophication because it can be installed at low cost and small area.
[발명의 구성 및 작용][Configuration and Function of Invention]
제1도는 본 발명의 개략적인 공정도를 보인 것으로서, 본 발명은 통상의 토양(土壤)에 과산화수소(H2O2), 차아염소산, 과산화물 중에 적어도 하나 이상을 첨가하는 공정과, 황산(H2SO2), 염산(HCl) 등의 무기산 중에 적어도 하나 이상을 첨가하는 공정과, 황산철(FeSO4, Fe2(SO4)3), 염화철(FeCl2, FeCl3), 황산알미늄(Al2(SO4)3), 황산칼슘(CaSO4), 염화칼슘(CaCl2) 중에 적어도 하나 이상을 첨가하는 공정과, 알카리 금속, 알카리 토류 금속의 수산화물, 탄산화물, 산화물을 소성 후의 pH가 중성에 가깝게 되도록 첨가하는 공정과, 철분을 첨가하는 공정, 그리고, 상기 혼합된 원료를 성형, 소성하는 공정 순으로 이루어 지는 바, 이하 본 발명 인 제거용 여재의 제조방법을 구체적인 실시예를 통하여 더욱 상세히 살펴 보면 다음과 같다.Figure 1 shows a schematic process diagram of the present invention, the present invention is a process for adding at least one or more of hydrogen peroxide (H 2 O 2 ), hypochlorous acid, peroxide to the soil, sulfuric acid (H 2 SO 2 ) adding at least one or more of inorganic acids such as hydrochloric acid (HCl), iron sulfate (FeSO 4 , Fe 2 (SO 4 ) 3 ), iron chloride (FeCl 2 , FeCl 3 ), aluminum sulfate (Al 2 ( SO 4 ) 3 ), adding at least one of calcium sulfate (CaSO 4 ) and calcium chloride (CaCl 2 ) and so that the pH after calcining hydroxides, carbonates and oxides of alkali metals and alkaline earth metals is close to neutral. The process of adding, the process of adding iron, and the process of molding and baking the mixed raw materials, the method of producing the present invention for removing the present invention in more detail through the following examples Same as
[실시예 1]Example 1
[제 1 공정- 토양분쇄공정][Step 1-Soil Crushing Process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니를 롤러분쇄기에 넣어 분쇄한 후 채로 돌맹이 등의 굵은 입자를 걸러내는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. It is a process of filtering the coarse particles such as boulder and the like after burning the wastes and wastes from various incineration plants and the activated sludge from various treatment plants in a roller mill.
[제 2 공정- 1차 첨가물 공급공정][Second process-primary additive supply process]
상기 제 1공정을 거친 갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 하수처리장에 있어서의 활성 오니에 대하여 유기체 탄소, 질소를 제거할 목적으로 과산화수소, 과산화물, 차아염소산을 첨가하는 공정이다.After using the charcoal, coal, etc. in the overall soil and thermal power plants, such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash soil group, construction residue, low quality soil, etc. It is a process that adds hydrogen peroxide, peroxide, hypochlorous acid to ashes and ashes from various incinerators and ashes from various incinerators and activated sludge in various sewage treatment plants for the purpose of removing organic carbon and nitrogen. .
가장 바람직한 것으로서는 과산화수소를 첨가하는 공정이다.Most preferred is the process of adding hydrogen peroxide.
상기 과산화수소의 첨가량은 일례로, 30%과산화수소의 경우에는 중량비로 건조 원료(토양,재 및 활성오니) 100% 에 대해서 1∼3%인 것이 가장 바람직하다.The amount of the hydrogen peroxide added is, for example, in the case of 30% hydrogen peroxide, the weight ratio is most preferably 1 to 3% based on 100% of the dry raw material (soil, ash and activated sludge).
[제 3 공정- 2차 첨가물 공급공정][3rd process- Secondary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 가운데서 산지에 따라 알루미늄 함유량이 많은 토양에 대하여 인산 제거능력의 향상을 목적으로 황산, 염산 등의 무기산을 첨가하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. It is a process of adding inorganic acids such as sulfuric acid and hydrochloric acid to improve the ability to remove phosphate from ash that comes out after burning garbage or wastes at various incinerators, and soils with high aluminum content, depending on the mountain area.
상기 무기산의 첨가량은 일례로, 10% 황산의 경우에는 중량비로 건조원료(토양,재 및 활성오니)100%에 대해서 10∼50% 인 것이 상술한 목적을 달성하는 데에 바람직하다.The addition amount of the inorganic acid is, for example, in the case of 10% sulfuric acid, it is preferable to achieve the above-mentioned object in a weight ratio of 10 to 50% with respect to 100% of the dry raw materials (soil, ash and activated sludge).
[제 4 공정- 3차 첨가물 공급공정][4th process-3rd additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와,각종 처리장에 있어서의 활성 오니 가운데서 알루미늄 함유량이 많은 원료에 대하여 황산제1철, 황산제2철, 염화제1철, 염화제2철, 황산알미늄, 황산칼슘, 염화칼슘 가운데에서 한 가지 이상을 첨가하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. For ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, and sulfuric acid for ashes from wastes and wastes burned at various incinerators and raw materials with high aluminum content among active sludges at various treatment plants. It is a process that adds one or more of aluminum, calcium sulfate, and calcium chloride.
상기 첨가량은 중량비로 건조원료(토양, 재 및 활성오니) 100%에 대해서 0-20%인 것이 바람직하다.The amount is preferably 0-20% by weight based on 100% of the dry raw materials (soil, ash and activated sludge).
[제 5 공정- 4차 첨가물 공급공정][5th process-4th additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니 가운데서 알루미늄 함유량이 많은 원료에 대하여 알칼리성 금속 또는 알칼리성 토류 금속의 산화물, 수산화물 또는 탄산화물을 소성 후의 pH가 중성이하가 되도록 첨가해 혼합하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. The pH after firing the oxides, hydroxides or carbonates of alkaline metals or alkaline earth metals for ashes produced after burning wastes or wastes at various incinerators and for raw materials with a high aluminum content among active sludges at various treatment plants is neutral. It is a process of adding and mixing as much as possible.
상기 공정에는 나트륨, 칼륨, 칼슘, 마그네슘 등의 산화물, 수산화물 또는 탄산화물 등이 있지만 이 가운데에서 생석회, 탄산석회 또는 소석회가 바람직하다.The process includes oxides such as sodium, potassium, calcium, magnesium, hydroxides or carbonates, but among them, quicklime, lime carbonate or slaked lime is preferred.
상기의 첨가량은 소성 후의 pH가 강산성이 되지 않도록 하는 양이다.The addition amount is an amount such that the pH after firing does not become strongly acidic.
pH가 강산성이 된 경우는 인산을 제거고정하는 철 이온이 수중(水中)에 용출해버려, 효과를 기대할 수 없다.When pH becomes strong acidic, iron ion which removes and fixes phosphoric acid elutes in water, and an effect cannot be expected.
첨가량은 중량비로 건조원료(토양, 재 및 활성오니) 100%에 대해서 2∼15% 인 것이 바람직하다.The addition amount is preferably 2 to 15% by weight based on 100% of the dry raw materials (soil, ash and activated sludge) by weight ratio.
[제 6 공정- 성형, 소성공정][Sixth Process-Molding, Firing Process]
제 1 공정∼제 4 공정의 완료 후에 예정한 형상으로 성형, 소성하는 공정이다.It is a process of shape | molding and baking to a predetermined shape after completion | finish of a 1st process-a 4th process.
성형방법은 형상에 따라 임의의 선택이 가능하며, 성형공정 및 혼합작업을 용이하게 하기 위하여 적당량의 물을 첨가할 수가 있다.The molding method can be arbitrarily selected depending on the shape, and an appropriate amount of water can be added to facilitate the molding process and mixing operation.
소성 조건은 원료 토양에 따라 다르지만 200∼500℃에서 2∼10분 정도가 바람직하다.The firing conditions vary depending on the raw material soil, but are preferably about 2 to 10 minutes at 200 to 500 ° C.
이러한 단시간의 소성조건은 원료토양 중의 구조수(構造水)를 제거하므로서 플러스 구조가 가능해 물과의 접촉면적 확대를 가능하게 하므로서 인산흡착의 기회가 많아지며, 현탁물질의 응집이 가능하게 된다.This short time firing condition allows a positive structure by removing the structural water in the raw soil, thereby increasing the contact area with water, thereby increasing the chance of phosphate adsorption and allowing the aggregation of suspended substances.
[실시예 2]Example 2
[제 1 공정- 토양분쇄공정][Step 1-Soil Crushing Process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 하수처리장에 있어서의 활성 오니 가운데서 알루미늄 함유량이 많은 원료를 롤러분쇄기에 넣어 분쇄한 후, 채로 돌맹이 등의 굵은 입자를 걸러내는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. It is a process to filter out coarse particles such as boulder and the like from ashes after burning trash or waste in various incinerators, and raw materials having a high aluminum content among the activated sludge in various sewage treatment plants.
[제 2 공정- 1차 첨가물 공급공정][Second process-primary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과, 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니 가운데서 산지에 따라 알루미늄 함유량이 많은 토양에 대하여 인산 제거능력의 향상을 목적으로 황산, 염산 등의 무기산을 첨가하는 공정이다.Ash from brown soil, red yellow forest soil, dark red soil group, gray brown soil group, volcanic ash soil group, construction soil and low soils, and charcoal and coal at the thermal power plant. And adding inorganic acids such as sulfuric acid and hydrochloric acid for the purpose of improving the phosphoric acid removal ability of ashes from burning incinerators after burning garbage and wastes, and soils with high aluminum content, depending on the region, among active sludges in various treatment plants. to be.
상기 공정의 처리는 상기 실시예 1의 제 3 공정과 같은 방법으로 행할 수가 있다.The process can be performed in the same manner as in the third process of the first embodiment.
[제 3 공정- 2차 첨가물 공급공정][3rd process- Secondary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니에 대하여 황산제1철, 황산제2철, 염화제1철, 염화제2철, 황산알미늄, 황산칼슘, 염화칼슘 가운데에서 한 가지 이상을 첨가하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. Regarding ash from burning wastes and wastes at various incinerators and activated sludge at various treatment plants, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, aluminum sulfate, calcium sulfate, and calcium chloride It is the process of adding one or more from the center.
상기 공정의 처리는 상기 실시예 1의 제 4 공정과 같은 방법으로 행할 수가 있다.The process can be performed in the same manner as in the fourth process of the first embodiment.
[제 4 공정- 3차 첨가물 공급공정][4th process-3rd additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과, 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니에 대하여 알칼리성 금속 또는 알칼리성 토류 금속의 산화물, 수산화물 또는 탄산화물을 소성 후의 pH가 중성이하가 되도록 첨가해 혼합하는 공정이다.Ash from brown soil, red yellow forest soil, dark red soil group, gray brown soil group, volcanic ash soil group, construction soil and low soils, and charcoal and coal at the thermal power plant. And ashes obtained after burning wastes or wastes at various incinerators, and mixed with an alkali metal or alkaline earth metal oxide, hydroxide or carbonate to be neutral so as to have a neutral pH after firing with respect to active sludge in various treatment plants. It is a process.
상기 공정에는 나트륨, 칼륨, 칼슘, 마그네슘 등의 산화물, 수산화물 또는 탄산화물 등이 있지만 이 가운데에서 생석회, 탄산석회 또는 소석회가 바람직하다.The process includes oxides such as sodium, potassium, calcium, magnesium, hydroxides or carbonates, but among them, quicklime, lime carbonate or slaked lime is preferred.
상기의 첨가량은 소성 후의 pH가 강산성이 되지 않도록 하는 양이다.The addition amount is an amount such that the pH after firing does not become strongly acidic.
pH가 강산성이 된 경우는 인산을 제거고정하는 철 이온이 수중(水中)에 용출해버려, 효과를 기대할 수 없다.When pH becomes strong acidic, iron ion which removes and fixes phosphoric acid elutes in water, and an effect cannot be expected.
상기 공정의 처리는 상기 실시예 1의 제 5 공정과 같은 방법으로 행할 수가 있다.The above process can be carried out in the same manner as the fifth process of the first embodiment.
상기 제 4 공정은 제 3 공정과 동시에 행하던지 또는 역 순서로 행할 수 가 있고, 상기의 제 2 공정, 제 3 공정 보다 우선 실시할 수 도 있다.The fourth step may be performed simultaneously with the third step or in the reverse order, and may be performed prior to the second step and the third step.
[제 5 공정- 성형, 소성공정][5th process-forming, firing process]
제 1 공정∼제 4 공정의 완료 후에 예정한 형상으로 성형, 소성하는 공정이다.It is a process of shape | molding and baking to a predetermined shape after completion | finish of a 1st process-a 4th process.
성형방법은 형상에 따라 임의의 선택이 가능하며, 성형공정 및 혼합작업을 용이하게 하기 위하여 적당량의 물을 첨가할 수 가 있다.The molding method can be arbitrarily selected according to the shape, and an appropriate amount of water can be added to facilitate the molding process and mixing operation.
상기 공정의 처리는 상기 실시예 1의 제 6 공정과 같은 방법으로 행할 수가 있다.The process can be performed in the same manner as in the sixth process of the first embodiment.
[실시예 3]Example 3
[제 1 공정- 토양분쇄공정][Step 1-Soil Crushing Process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 하수처리장에 있어서의 활성 오니를 롤러분쇄기에 넣어 분쇄한 후 채로 돌맹이 등의 굵은 입자를 걸러내는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. It is a process for filtering coarse particles such as boulder and the like after ashes from various incineration plants are burned with waste and waste, and activated sludge from various sewage treatment plants is put in a roller mill.
[제 2 공정- 1차 첨가물 공급공정][Second process-primary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니에 대하여 황산제1철, 황산제2철, 염화제1철, 염화제2철, 황산알미늄, 황산칼슘, 염화칼슘 가운데에서 한 가지 이상을 첨가하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. Regarding ash from burning wastes and wastes at various incinerators and activated sludge at various treatment plants, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, aluminum sulfate, calcium sulfate, and calcium chloride It is the process of adding one or more from the center.
상기 공정의 처리는 상기 실시예 1의 제 4 공정과 같은 방법으로 행할 수가The above process can be carried out in the same manner as the fourth process of the first embodiment.
있다.have.
[제 3 공정- 2차 첨가물 공급공정][3rd process- Secondary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니에 대하여 알칼리성 금속 또는 알칼리성 토류 금속의 산화물, 수산화물 또는 탄산화물을 소성 후의 pH가 중성이하가 되도록 첨가해 혼합하는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. A process of adding and mixing an alkali metal or alkaline earth metal oxide, hydroxide, or carbonate so that the pH after firing is lower than the ash generated after burning garbage or waste in various incineration plants and activated sludge in various treatment plants. to be.
상기 공정의 처리는 상기 실시예 1의 제 5 공정과 같은 방법으로 행할 수가 있다.The above process can be carried out in the same manner as the fifth process of the first embodiment.
상기 제 3 공정은 제 2 공정과 동시에 행하던지 또는 역 순서로 행할 수가 있고, 제 3 공정 보다 우선 실시할 수 도 있다.The third step may be performed simultaneously with the second step or in the reverse order, or may be performed prior to the third step.
[제 4 공정- 성형, 소성공정][4th process-molding, firing process]
제 1 공정∼제 3 공정의 완료 후에 예정한 형상으로 성형, 소성하는 공정이다.It is a process of shape | molding and baking to a predetermined shape after completion | finish of a 1st process-a 3rd process.
성형방법은 형상에 따라 임의의 선택이 가능하며, 성형공정 및 혼합작업을 용이하게 하기 위하여 적당량의 물을 첨가할 수가 있다.The molding method can be arbitrarily selected depending on the shape, and an appropriate amount of water can be added to facilitate the molding process and mixing operation.
상기 공정의 처리는 상기 실시예 1의 제 6 공정과 같은 방법으로 행할 수가 있다.The process can be performed in the same manner as in the sixth process of the first embodiment.
[실시예 4]Example 4
[제 1 공정- 토양분쇄공정][Step 1-Soil Crushing Process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 하수처리장에 있어서의 활성 오니를 롤러분쇄기에 넣어 분쇄한 후 채로 돌맹이 등의 굵은 입자를 걸러내는 공정이다.Ash and ash that are produced after using charcoal and coal as fuel in the whole soil and thermal power plants such as brown forest soil group, red yellow forest soil group, dark red soil group, gray brown soil group, volcanic ash group, construction residue and low quality soil. It is a process for filtering coarse particles such as boulder and the like after ashes from various incineration plants are burned with waste and waste, and activated sludge from various sewage treatment plants is put in a roller mill.
[제 2 공정- 1차 첨가물 공급공정][Second process-primary additive supply process]
갈색산림토양군, 적황색산림토양군, 암적색토양군, 회갈색토양군, 화산회토양군, 건설잔토, 저질토 등의 토양 전반과, 화력발전소등에서 목탄, 석탄 등을 연료로 사용한 후 나오는 재(Ash) 및 각종 소각장에서 쓰레기나 폐기물 등을 태운후 나오는 재와, 각종 처리장에 있어서의 활성 오니에 대하여 황산제1절, 황산제2철, 염화제1철, 염화제2철, 황산알미늄, 황산칼슘, 염화칼슘 가운데에서 한 가지 이상을 첨가하는 공정이다.Ash from brown soil, red yellow forest soil, dark red soil group, gray brown soil group, volcanic ash soil group, construction soil and low soils, and charcoal and coal at the thermal power plant. And ashes from burning incinerators and wastes from various incinerators, and activated sludge from various treatment plants. Section 1, ferric sulfate, ferrous chloride, ferric chloride, aluminum sulfate, calcium sulfate, It is a process that adds one or more of calcium chloride.
상기 공정처리는 상기 실시예 1의 제 4 공정과 같은 방법으로 행할 수가 있다.The said process can be performed by the method similar to the 4th process of the said Example 1.
[제 3 공정- 성형, 소성공정][3rd process-molding, firing process]
제 1 공정∼제 2 공정의 완료 후에 예정한 형상으로 성형, 소성하는 공정이다.It is a process of shape | molding and baking to a predetermined shape after completion | finish of a 1st process-a 2nd process.
성형방법은 형상에 따라 임의의 선택이 가능하며, 성형공정 및 혼합작업을 용이하게 하기 위하여 적당량의 물을 첨가할 수가 있다.The molding method can be arbitrarily selected depending on the shape, and an appropriate amount of water can be added to facilitate the molding process and mixing operation.
상기 공정처리는 상기 실시예 1의 제 6 공정과 같은 방법으로 행할 수가 있다.The said process can be performed by the method similar to the 6th process of the said Example 1.
[실시예 5]Example 5
상기의 실시예 1 ∼ 4에 기재한 인 제거용 여재의 제조 방법에 있어서 인산의 제거능력 향상을 위하여 성형 전의 원료 혼합물에 철분을 첨가하는 공정이다.It is a process of adding iron powder to the raw material mixture before shaping | molding in order to improve the removal ability of phosphoric acid in the manufacturing method of the phosphorus removal media described in Examples 1-4 mentioned above.
철분의 첨가량은 성형 전의 건조토양 100%에 대해서 5∼20% 인 것이 바람직하다.The amount of iron added is preferably 5 to 20% with respect to 100% of the dry soil before molding.
상기의 인 제거용 여재는, 사용방법에 따라 그 형상과 크기를 적절히 선택할 수 있으며, 0. 6∼20mm의 구형 (球刑)의 입상(粒狀) 또는 과립물(顆粒物)이 바람직하다.The shape and size of the above-mentioned phosphorus removal medium can be suitably selected according to a usage method, and spherical granules or granules of 0.6-20 mm are preferable.
물과의 접촉 면적 확대와 미립자의 여과기능을 높이는 의미에서 공극율(입상물 체적에 대한 공극이 차지하는 비율)60% 이하와 다공질이 바람직하다.The porosity (the ratio of the pore to the granular volume) of 60% or less and the porous are preferable in the sense of expanding the contact area with water and improving the filtration function of the fine particles.
이하에 상기 각 실시예에 의한 본 발명을 더욱 상세히 살펴보면 다음과 같다.Looking at the present invention according to the above embodiments in more detail as follows.
[실시예 1 의 실험예 1∼3 및 비교예 1∼3][Experimental Examples 1-3 and Comparative Examples 1-3 of Example 1]
실시예 1의 각 원료 토양 (표 1에 나타낸 각 원료 토양) 100g에 30% 과산화수소 3g을 첨가한 다음, 10% 황산 40㎖를 첨가했다. 그리고 황산제1철 20g을 첨가한 후, 소석회 10g을 첨가해 반죽하였다.3 g of 30% hydrogen peroxide was added to 100 g of each raw material soil of Example 1 (each raw material soil shown in Table 1), followed by 40 ml of 10% sulfuric acid. Then, after adding 20 g of ferrous sulfate, 10 g of calcined lime was added and kneaded.
그 후에 직경 약 5.0mm 크기로 조립(造粒), 성형한 다음 실험용 전기로를 이용해 400℃에서 5분간 소성하였다.Thereafter, the granules were granulated and molded to a size of about 5.0 mm, and then fired at 400 ° C. for 5 minutes using an experimental electric furnace.
상기 공정으로 얻어진 시료와 비교용 시료를 사용하여 표 1과 같이 인산, 탄소, 질소의 제거시험을 행하였으며, 비교예의 시료도 실험예의 시료와 같은 조건으로 소성했다.Using the sample obtained by the said process and the comparative sample, the removal test of phosphoric acid, carbon, and nitrogen was performed like Table 1, The sample of the comparative example was also baked on the conditions similar to the sample of an experimental example.
결과와 각 시료의 성상을 다음의 표 1에 정리했다.The results and the properties of each sample are summarized in Table 1 below.
[표 1]TABLE 1
[실시예 1]Example 1
표 1에서 밝혀진 것처럼 각 실험예의 인산 제거력은 비교예보다 우월한 결과를 얻었다.As is clear from Table 1, the phosphate removal ability of each experimental example was superior to that of the comparative example.
또한, 실험예 시료의 인산 제거의 지속성을 평가하기 위하여 실험 종료 후 순수(水)에 24시간 방치하였으나 순수(水)에서 인산은 검출되지 않았다.In addition, in order to evaluate the persistence of phosphoric acid removal of the test sample, the sample was left in pure water for 24 hours, but no phosphoric acid was detected in the pure water.
[실시예 2 의 실험예 4∼6 및 비교예 4∼6][Experimental Examples 4-6 and Comparative Examples 4-6 of Example 2]
실시예 2의 각 원료 토양(표 2에 나타낸 각 원료 토양) 100g에 10% 황산 40㎖을 첨가한 후 소석회 10g과 황산제1철 20g을 첨가하여 반죽했다.40 ml of 10% sulfuric acid was added to 100 g of each raw material soil (each raw material soil shown in Table 2), followed by kneading by adding 10 g of calcined lime and 20 g of ferrous sulfate.
그리고 직경 5.0mm 크기로 조립 (造粒)성형한 다음 실험용 전기로를 이용하여 400℃에서 5분간 소성했다.Then, the granules were granulated to a size of 5.0 mm in diameter, and then fired at 400 ° C. for 5 minutes using an experimental electric furnace.
상기 공정으로 얻어진 시료와 비교용 시료를 사용하여 표 1과 같이 인산의 제거시험을 행하였으며, 비교예의 시료도 실험예의 시료와 같은 조건으로 소성했다.Using the sample obtained by the said process and the comparative sample, the removal test of phosphoric acid was performed like Table 1, and the sample of the comparative example was also baked on the conditions similar to the sample of an experimental example.
결과와 각 시료의 성상을 다음의 표 2에 정리했다.The results and the properties of each sample are summarized in Table 2 below.
[표 2]TABLE 2
[실시예 2]Example 2
표 2에서 나타난 바와 같이 각 실험예의 인산 제거력은 비고예보다 우월한 결과를 얻었다.As shown in Table 2, the phosphate removal ability of each experimental example was superior to the remarkable example.
[실시예 3의 실험예 7-9 및 비교예 7∼9]Experimental Example 7-9 of Comparative Example 3 and Comparative Examples 7-9
실시예 3 의 각 원료 토양(표3에 나타낸 각 원료토양) 100g에 황산제1철 27g을 첨가한 다음 소석회 10g과 물 120cc를 첨가해 반죽했다.To 100 g of each raw material soil (each raw material soil shown in Table 3) of Example 3, 27 g of ferrous sulfate was added, followed by kneading with 10 g of calcined lime and 120 cc of water.
그 후에 직경 5.0mm 크기로 조립 (造粒)한 다음 실험용 전기로를 이용하여 400℃에서 5 분간 소성하였다.Thereafter, it was granulated to a size of 5.0 mm in diameter and then fired at 400 ° C. for 5 minutes using an experimental electric furnace.
표 3과 같이 인산의 제거 시험을 행하였으며, 비교예에 사용한 시료도 인 제거용 여재와 같은 조건으로 소성했다.The removal test of phosphoric acid was performed like Table 3, and the sample used for the comparative example was also baked on the conditions similar to the medium for phosphorus removal.
결과와 각 시료의 성상을 다음의 표 3에 정리했다.The results and the properties of each sample are summarized in Table 3 below.
[표 3]TABLE 3
[실시예 3]Example 3
표 3에서 나타난 바와 같이 각 실험예의 인산 제거력은 비교예보다 우월한 결과를 얻었다.As shown in Table 3, the phosphate removal power of each experimental example was superior to that of the comparative example.
[실시예 4의 실험예 10∼12 및 비교예 10∼12][Experimental Examples 10-12 and Comparative Examples 10-12 of Example 4]
실시예 5의 각 원료 토양(표 4에 나타낸 각 원료토양) 100g에 황산칼슘 5g과 황산제1철 15g을 첨가했다.To 100 g of each raw material soil (each raw material soil shown in Table 4) of Example 5, 5 g of calcium sulfate and 15 g of ferrous sulfate were added.
그 후에 직경 5.0mm 크기로 조립(造粒)성형한 다음 실험용 전기로에서 400℃에서 5분간 소성했다.Thereafter, the granules were granulated to a size of 5.0 mm in diameter and then fired at 400 ° C. for 5 minutes in an experimental electric furnace.
이 공정으로 얻어진 시료와 비교용 시료를 사용하여 표 4와 같이 인산의 제거시험을 행하였으며, 비고예에 사용한 시료도 인 제거용 여재와 같은 조건으로 소성하였다.Using the sample obtained in this step and the comparative sample, the phosphoric acid removal test was performed as shown in Table 4, and the sample used in the remarks example was also fired under the same conditions as the media for phosphorus removal.
결과와 각 시료의 성상을 다음의 표 4에 정리했다.The results and the properties of each sample are summarized in Table 4 below.
[표 4]TABLE 4
[실시예 4의 순서][Sequence of Example 4]
표 4에서 나타난 바와 같이 각 실험예의 인산 제거력은 비고예보다 우월한 결과를 얻었다.As shown in Table 4, the phosphate removal ability of each experimental example was superior to the remarkable example.
[실시예 5 의 실험예 13∼16]Experimental Examples 13 to 16 of Example 5
실험예 1, 실험예 4, 실험예 7, 실험예 10의 성형 공정 전의 중간 처리 원료에 다음의 표 5에 표시한 철분 양을 첨가한 후 실험예 1과 같이 성형 소성한 시료를 철분 무첨가(비교예)의 시료와 비교했다.After adding the iron amounts shown in the following Table 5 to the intermediate raw material before the molding step of Experimental Example 1, Experimental Example 4, Experimental Example 7, Experimental Example 10, and adding the iron powder to the sample calcined and molded as in Experimental Example 1 It compared with the sample of Example).
결과와 시료의 성상을 표 5에 정리했다.The results and the properties of the samples are summarized in Table 5.
[표 5]TABLE 5
표 5에서 나타난 바와 같이 철분을 첨가한 경우 약 20% 인산 제거력이 기초 실험예(비교예)보다 우월한 결과를 얻었다.As shown in Table 5, when iron was added, about 20% phosphoric acid removal power was superior to the basic experimental example (comparative example).
이상과 같은 본 발명의 제조 방법에 의하여 얻어진 인 제거용 여재는 수중에 투입하므로서 직접 인산을 포착하는데 사용할 수가 있으며 필요에 의해 적당한 용기에 충진하거나 기존의 수처리 방식과 연계하여 사용할 수 가 있다.Phosphorus removal media obtained by the production method of the present invention as described above can be used to directly capture the phosphoric acid by adding to the water, can be filled in a suitable container if necessary, or can be used in connection with the existing water treatment method.
또한, 관(菅)에 충진하여 통수처리용으로 사용하면 인 제거와 동시에 여과재, 현탁물질의 응집재로서도 사용할 수가 있다.In addition, when the tube is filled with water and used for water treatment, it can be used as a filter medium and a flocculant of a suspended substance at the same time as phosphorus removal.
상기 각 실시예에서 여재에 포함된 황산 칼슘에서 용해되어 나오는 칼슘 이온(Ca2+)이 물 속에 용해되어 있는 인산 이온 등과 반응하여 인산 칼슘 등의 화합물이 생성되고 이렇게 생성된 인 화합물은 여재의 미세한 공극 속 또는 표면에 흠착, 여과되어 재 용출되지 않는다.In each of the above embodiments, calcium ions (Ca 2+ ) dissolved in calcium sulfate in the media are reacted with phosphate ions, etc. dissolved in water to produce compounds such as calcium phosphate. It is not scratched or filtered in the voids and is not redissolved.
또한, 정인산(Orthophosphate)보다 화학반응성이 떨어지는 플리인산염(Pol yphosphate) 및 유기인(Organic phosphorus) 등은 여재의 미세한 공극 속 또는 표면에 흡착, 여과된다.In addition, polyphosphate and organic phosphorus, which are less chemically reactive than orthophosphate, are adsorbed and filtered in the fine pores or surfaces of the media.
칼슘 이온(Ca2+)은 여러 형태의 인산 이온 등과 반응하여 다음의 화학식 1과 같이 여러 종류의 인산 칼슘(Calcium Phosphate)의 침전물을 형성한다.Calcium ions (Ca 2+ ) react with various types of phosphate ions to form precipitates of various types of calcium phosphate (Calcium Phosphate), as shown in the following Chemical Formula 1.
[화학식 1][Formula 1]
Ca2++ HPO4 2-→ CaHPO4(Calcium hydrogen phosphate), pKsp = 6.66Ca 2+ + HPO 4 2- → CaHPO 4 (Calcium hydrogen phosphate), pKsp = 6.66
Ca2++ 2HPO4 -→ Ca(H2PO4)2(Calcium hydrogen phosphate), pKsp = 1.14 Ca 2+ + 2HPO 4 - → Ca (H2PO 4) 2 (Calcium hydrogen phosphate), pKsp = 1.14
3Ca2++ 2PO4 3-→ Ca3(PO4)2(β-Tricalcium phosphate), pKsp = 24.03Ca 2+ + 2PO 4 3- → Ca 3 (PO 4 ) 2 (β-Tricalcium phosphate), pKsp = 24.0
5Ca2++ 3PO4 3-+ OH-→ Ca5(PO4)3OH(Hydroxyapatite), pKsp = 55.9 5Ca 2+ + 3PO 4 3- + OH - → Ca 5 (PO 4) 3 OH (Hydroxyapatite), pKsp = 55.9
다음은 상기 실시예 1에 따른 인 제거용 여재의 표본을 발췌, 그 데이터를 기술한 것이다.The following is a sample of the phosphorus removal medium according to Example 1, and describes the data.
1) 인 제거능: 인 제거용 여재 1kg당 평균 19.6g의 인(燐:Phosphorus)을 제거1) Phosphorus removal ability: Remove 19.6g of Phosphorus per 1kg of phosphorus removal media
측정조건: 25℃, 1% 인산(P2O5)용액 : 여재 = 50 : 1Measurement condition: 25 ℃, 1% phosphoric acid (P 2 O 5 ) solution: media = 50: 1
2) 포화투수속도' 0.35∼0.45cm/sec.2) Saturation permeation rate '0.35 ~ 0.45 cm / sec.
측정방법 : 정수위 법Measuring Method: Water Purification Method
3) 중량 : 1.90∼2.35g/㎤3) Weight: 1.90 ~ 2.35g / cm 3
4) 소성물내 공극율 : 55∼75%4) Porosity in the fired product: 55 ~ 75%
5) 입도5) particle size
1.0- 10.0mm1.0-10.0mm
6) 안정성6) stability
3개월간 통수시킨후 용적변화가 거의 없었음.Little change in volume after 3 months of water flow.
7) 인 제거 성능실험7) Phosphorus removal performance test
다음의 표 6, 표 7 과 같다.Table 6 and Table 7 below.
[표 6]TABLE 6
인 제거용 여재량 20gPhosphorus removal medium 20g
Column test height 20cmColumn test height 20cm
연속 투과 속도 300㎖/hrContinuous permeation rate 300ml / hr
SV치=투과수량(㎥/hr)/제거재량(㎥), 통수 24시간후의 측정결과SV value = permeated water (㎥ / hr) / removable material (㎥), measurement result after 24 hours of water flow
[표 7]TABLE 7
인 제거용 여재량 20gPhosphorus removal medium 20g
Column test height 20cmColumn test height 20cm
연속 투과 속도 200㎖/hrContinuous permeation rate 200ml / hr
SV치=투과수량(㎥/hr)/제거재량(㎥), 통수 24시간후의 측정결과SV value = permeated water (㎥ / hr) / removable material (㎥), measurement result after 24 hours of water flow
이상과 같은 본 발명은,The present invention as described above,
1) 인 제거용 여재는 다공도 입상형태로 인 제거용 여재를 넣은 여과조에 물을 통과시키거나 물 속에 직접 침적시키는 것으로도 조류 번식의 제한인자인 인이 화학적 결합및 흡착, 여과되어 제거된다.1) Phosphorus removal media is a porous granular form, through which water is passed through a filtration tank containing phosphorus removal media or deposited directly in water to remove phosphorus, which is a limiting factor for algae breeding, by chemical bonding, adsorption, and filtration.
2) 인 제거용 여재는 일반적인 제거방법으로 제거가 불가능한 저농도(0. 1ppm이하)부터 고농도의 인을 함유한 공장폐수 및 하수, 오수의 2차, 3차 처리수 속의 인을 효과적으로 제거한다.2) Phosphorus removal media effectively removes phosphorus from low concentrations (less than 0.1 ppm) which cannot be removed by general removal methods, from plant wastewater containing high concentrations of phosphorus, sewage, and secondary and tertiary treated water.
3) 투수계수는 0.5∼2.0cm/sec정도이며 투수속도를 보다 빠르게 하는 것도 가능하다.3) Permeability coefficient is about 0.5 ~ 2.0cm / sec and it is also possible to make permeation speed faster.
4) 인 제거용 여게 1㎥당 1일 240㎥를 통수(SV=10)시켜도 인산을 효과적으로 단시간에 제거한다.4) Phosphoric acid can be effectively removed in a short time even though 240㎥ of water per 1㎥ per day of phosphorus removal (SV = 10).
5) 인 제거용 여재 1kg당 평균 인(P) 제거량은 20g이상으로 제거율이 높다.5) The average removal rate of phosphorus (P) per kg of phosphorus removal media is more than 20g and the removal rate is high.
(실험실에서의 최대 인 제거량은 여재 1kg당 36g이었음.)(The maximum phosphorus removal in the laboratory was 36g per kg of media).
6) 다공질이기 때문에 인산과 반응하여 생성된 인 화합물 등은 여재의 공극 중 또는 표면에 제거, 여과되어 유출하지 않을 뿐 만 아니라 오니도 발생하지 않는다.6) Because it is porous, the phosphorus compound produced by reaction with phosphoric acid does not flow out of the media or in the surface of the media and is not filtered out, and no sludge occurs.
7) 인 제거용 여재를 사용하면 설비를 소형화할 수 있고 오니처리 등의 관리비를 절감시킬 수 있다.7) The use of phosphorus removal media can reduce the size of equipment and reduce the management cost of sludge treatment.
8) 인 제거용 여재의 제거능력이, 물 속에 함유된 각종 부유물질에 의해 오염되어, 저하될 시점에 공기로 폭기시킨 후 역세하여 재사용을 할 수 있다.8) The removal capacity of phosphorus removal media is contaminated by various suspended substances contained in water, and it can be aerated and reused after aeration with air at the time when it is lowered.
9) 슬러지(Sludge)의 발생 등으로 인한 제2의 환경오염이 전혀없을 뿐 만 아니라, 완전히 사용한 후에는 고성능 원예용토 및 토지개량재 등으로 사용할 수 있고, 흡착된 인산 성분으로 고성능 비료로서 활용할 수 있다.9) Not only does it have no second environmental pollution due to sludge generation, but also it can be used as a high-performance horticultural soil and land improvement material after fully used, and it can be utilized as a high-performance fertilizer with the adsorbed phosphoric acid component. have.
[발명의 효과][Effects of the Invention]
이상과 같이 본 발명은 국내에서 쉽게 공급받을 수 있는 토양(土壤)에 과산화수소(H2O2), 차아염소산, 과산화물, 황산(H2SO4), 염산(HCl), 황산철(FeSO4, Fe2(SO4)3), 염화철(FeCl2, FeCl3), 황산알미늄(Al2(SO4)3), 황산칼슘(CaSO4), 염화칼슘(CaCl2) 알카리 금속, 알카리 토류 금속의 수산화물, 탄산화물, 산화물 등을 주 원료로 한 인 흡착제를 제공하므로서 안정적인 생산과 가격와 저렴화를 도모할 수 있게 됨은 물론 생산설비 역시 간이하여 부영양화의 문제가 심각한 하천과 소호(沼湖) 등에 폭 널게 이용할 수 있는 것으로, 본 발명은 상기 언급한 바 외에도 예상외의 여러 경제적, 환경적 가치등이 기대되는 것이다.As described above, the present invention provides hydrogen peroxide (H 2 O 2 ), hypochlorous acid, peroxide, sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), iron sulfate (FeSO 4 ,) in soil that can be easily supplied in Korea. Fe 2 (SO 4 ) 3 ), iron chloride (FeCl 2 , FeCl 3 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), calcium sulfate (CaSO 4 ), calcium chloride (CaCl 2 ) alkali metal, alkali earth hydroxide By providing phosphorus adsorbents based on carbon, oxides, oxides, etc., it is possible to achieve stable production, price, and cost reduction, and its production facilities are also simple, so it can be widely used in rivers and lakes, where the problem of eutrophication is serious. As mentioned above, the present invention is expected to have various unexpected economic and environmental values in addition to the above.
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KR100535437B1 (en) * | 1998-07-01 | 2006-02-28 | 양대윤 | Liquid water purifier with a mixture of calcium oxide and ocher |
KR101325091B1 (en) * | 2008-01-30 | 2013-11-06 | 엘켐 솔라 에이에스 | How to produce calcium compounds |
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JPS59154186A (en) * | 1983-02-21 | 1984-09-03 | Ikuo Murakami | Sewage treatment |
JPH08229548A (en) * | 1995-02-27 | 1996-09-10 | Hoei:Kk | Water purifying block |
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JPS59154186A (en) * | 1983-02-21 | 1984-09-03 | Ikuo Murakami | Sewage treatment |
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KR100535437B1 (en) * | 1998-07-01 | 2006-02-28 | 양대윤 | Liquid water purifier with a mixture of calcium oxide and ocher |
KR101325091B1 (en) * | 2008-01-30 | 2013-11-06 | 엘켐 솔라 에이에스 | How to produce calcium compounds |
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